Aqueous liquid cleaning compositions and their use

ABSTRACT

An isotropic aqueous liquid detergent composition comprising: a succinate dimer surfactant selected from alkyl and alkenyl succinate dimers in which two succinic acid moieties or derivatives thereof are joined by a (poly)alkyleneoxy bridge and each carboxylic acid group is independently in the free acid form, salt form or is esterified or is a corresponding amide group; and mixtures thereof; one or more other surfactants; and water.

FIELD OF INVENTION

The present invention relates to aqueous liquid cleaning compositions.It also relates to methods of using such compositions for the cleaningof fabrics.

BACKGROUND OF INVENTION

Aqueous liquid detergent compositions can generally be considered tofall into one of two categories, namely isotropic or structured.Structured compositions usually contain lamellar phases formed ofsurfactant and water, which cause them to be relatively viscous, shearthinning and often, to have solid suspending properties. Isotropiccompositions, on the other hand, usually have a viscosity similar tothat of water and are substantially Newtonian. In addition, consumersgenerally prefer isotropic compositions to be substantially transparent,or at least, translucent.

Lack of clarity in such aqueous liquid detergent compositions can be theresult of a number of factors. One such factor is the formation ofmicellar or more ordered phases. Another cause of loss of clarity ispotentially due to instability of one or more ingredients. Suchinstability can be due to the presence of highly reactive species, suchas bleach catalysts, for example, of the type used to catalyse bleachingby atmospheric oxygen. It can also be due to species which degrade tooreadily. Reactive species can attack and degrade organic moleculeswithin the formulation. An example of an ingredient of the kind whichdegrades very easily is enzymes.

In isotropic aqueous liquid detergent compositions, it is common toinclude one or more hydrotropes such as ethanol, sodium xylenesulphonate (SXS) or sodium cumene sulfonate (SCS), as well aspolypropylene glycol (PPG). These materials have the function ofinhibiting the formation of ordered phases and so promote the clarity ofthe liquid. However, they are relatively costly and do not reallycontribute to the leaning performance of the product.

It is also common to use organic bases to neutralise fatty acids, inorder to result in the formation of a more soluble soap. Such basis aretypically, monoethanolamine or triethanolamine. Using these organicbases as the cation in a soap and/or adding an organic base when a soapis present, can stabilise the formulation at low temperatures. However,these materials have the potential disadvantage of inducing colourinstability at higher temperatures.

Thus, the use of hydrotropes has a cost penalty in formulation of theproduct. The use of organic bases as stabilisers for soap can promoteinstability at high temperatures.

There is therefore a need to find an alternative form of stabiliserwhich does not carry such a cost penalty and/or does not havedisadvantages to the same degree as conventional stabilisers. To helpavoid the cost penalty disadvantage, it would be helpful to utilise astabiliser which has another useful function in the formulation. Forexample, if such an alternative stabiliser were a surfactant, it wouldcontribute to the cleaning performance of the product.

We have now found that succinate dimer, optionally including derivativesthereof, surfactants may fulfil this role of detergent (surfactant)active and stabiliser.

In liquid detergent compositions, alkyl and alkenyl disuccinates havebeen mentioned as possible detergency builders, as disclosed inUS-A-25/0124,528. Alkyl and alkenyl succinates have been disclosed asbuilders for liquid detergents, according to U.S. Pat. No. 5,945,394.Long chain (di)-alk(en)yl succinates have been disclosed as usefulsurfactant ingredients in aqueous liquid detergent compositions in manyprior documents such as GB-A-2 232 420, GB-A-2 120 272, EP-A-476 212,EP-A-241 073, EP-A-212 713, EP-A-200 263, EP-A-233 306 and EP-A-028 850.These materials have also been disclosed as possible ingredients forfabric conditioner compositions, as disclosed in WO-A-99/27056.

Alkyl succinates and unsubstituted tartrate succinate builders have beendescribed as such in EP-A-342 177.

SUMMARY OF INVENTION

A first aspect of the invention provides an isotropic aqueous liquiddetergent composition comprising:

a succinate dimer surfactant as specified in claim 1; one or more othersurfactants; and water.

A second aspect of the present invention provides a method ofpreparation of an isotropic aqueous liquid detergent composition, themethod comprising admixture of water, one or more other surfactants anda succinate dimer surfactant of the invention.

A third aspect of the present invention provides use of a succinatedimer surfactant according to the present invention as a stabiliser inan isotropic aqueous liquid detergent composition, the composition alsocomprising one or more other surfactants and water.

DETAILED DESCRIPTION OF THE INVENTION

The Succinate Dimer Surfactant

The succinate dimer surfactant present in the composition of theinvention comprises or consists of at least one compound of formula (I):

wherein in formula (I), each of R¹ and R² is independently selected fromalkyl and alkenyl groups having from 8 to 18, preferably from 12 to 18,most preferably 18 carbon atoms; each of R³ and R⁴ is independentlyselected from hydrogen, groups M where M is a metal counter-cation,preferably an alkali metal such as sodium, C₁-C₆, preferably C₁-C₄ alkylgroups and groups of formula —NR⁶R⁷ where R⁶ and R⁷ are independentlyselected from hydrogen and C₁-C₆, preferably C₁-C₄ alkyl groups; and

R⁵ is selected from poly(alkyleneoxy) groups, preferably groups offormula —(C_(n)H_(2n+1)O)_(m)—C_(n)H_(2n+1)— where m is from 0 to 12,

preferably from 6 to 10, more preferably from 8 to 10, most preferably10 wherein in each C_(n)H_(2n+1) moiety n is independently from 2 to 4,more preferably 2 and preferably also, each n is the same.

In some preferred embodiments, R¹ and R² are independently selected fromgroups of formula CH₃—(CH₂)_(p)—CH═CH—CH₂— where p is preferably from 4to 14, more preferably from 8 to 14 and most preferably is 14.

In some preferred embodiments, R¹ and R² are the same as each other andR³ and R⁴ are the same as each other, most preferably both hydrogen orboth —O⁻M⁺.

Preferably also, the composition of the invention comprises from 0.1% to5%, more preferably from 0.2% to 3%, most preferably from 0.5% to 2% byweight of the succinate dimer surfactant. However, there is no specificlimitation on level and it could constitute, for example, from 0.001% to15% or 0.005% to 10% by weight of the composition.

Compounds of formula (I) can be readily prepared by the followinggeneric procedure using well known textbook chemistry. Alkenyl-succinicanhydride precursors are commercially available (e.g. ex Aldrich) or canbe prepared via the “ene reaction” by reaction of an alkene with maleicanhydride (J. March, Advanced Organic Chemistry pg 711, 3^(rd) Edn. 1984and references cited). If required, the double bond in the alkenylgroupcan be hydrogenated using catalytic hydrogenation (J. March, AdvancedOrganic Chemistry pg 691, 3rd ed. 1984 and references cited). Thealkenyl-succinic anhydrides are converted to the mono-ester/diester mixvia ring-opening of the anhydride by reaction with one or both alcoholendgroups of a polyethyleneglyccol of choice (J. March, Advanced OrganicChemistry pg 347, 3^(rd). Edn. 1984 and references cited). The ratio ofmono/diester can be influenced by varying the molar ratio of anhydrideto polyethyleneglycol. Reaction of 2 equivalents of anhydride with oneequivalent of polyethyleneglycol would give the most economic ratio ofnon-reacted started materials with the products mono-ester and di-ester.The reaction can be done without solvent and can be followed by infraredspectroscopy by monitoring the disappearance of the anhydride carbonylstretch vibration absorption at 1860 cm⁻¹ and formation of estercarbonyl stretch vibration absorption 1733 cm⁻¹.

The Water

The compositions according to the present invention preferably alsocomprise from 30% to 90%, more preferably from 40% to 85%, mostpreferably from 50% to 80% by weight of the water.

Other Surfactant

The compositions of the present invention comprise one or moresurfactants other than the succinate dimer. Based on the weight of thetotal composition such other surfactant(s) preferably are from 5 to 60%,more preferably from 10 to 50% by weight of one or more othersurfactants preferably selected from anionic, nonionic, cationic,zwitterionic active detergent material or mixtures thereof.

Non-limiting examples of such other surfactants useful herein typicallyat levels from about 10% to about 70%, by weight, include theconventional C10-C18 e.g. C10 to C13 alkylbenzene sulphonates (“LAS”),the C10-C18 secondary (2,3) alkyl sulphates of the formulaCH3(CH2)_(x)(CHOS03-M+)CH3 and CH3(CH2)_(y)(CHOS03-M+)CH2CH3 where x and(y+1) are integers of at least about 7, preferably at least about 9, andM is a water-solubilising cation, especially sodium, unsaturatedsulphates such as oleyl sulphate, C10-C18 alkyl alkoxy carboxylates(especially the EO 1-7 ethoxycarboxylates), the C10-C18 glycerol ethers,the C10-C18alkyl polyglycosides and their corresponding sulphatedpolyglycosides, and C12-C18 alpha-sulphonated fatty acid esters. Ifdesired, the conventional nonionic and amphoteric surfactants such asthe C12-C18 alkyl ethoxylates (“AE”) including the so-called narrowpeaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especiallyethoxylates and mixed ethoxy/propoxy), C12-C18 betaines andsulphobetaines (“sultaines”), C10-C18 amine oxides, and the like, canalso be included in the overall compositions. The C10-C18 N-alkylpolyhydroxy fatty acid amides can also be used. Typical examples includethe C12-C18 N-methylglucamides. See WO 9,206,154. Other sugar-derivedsurfactants include the N-alkoxy polyhydroxy fatty acid amides, such asC10-C18 N-(3-methoxypropyl)glucamide. C10-C20 conventional soaps mayalso be used. If high sudsing is desired, the branched-chain C10-C16soaps may be used.

Mixtures of anionic and nonionic surfactants are especially useful.Other conventional useful surfactants are listed in standard texts.

Other anionic surfactants useful for detersive purposes can also beincluded in the isotropic compositions hereof. These can include salts(including, for example, sodium potassium, ammonium, and substitutedammonium salts such a mono-, di- and triethanolamine salts) of soap,C9-C20 linear alkylbenzenesulphonates, C8-C22 primary or secondaryalkanesulphonates, C8-C24 olefinsulphonates, sulphonated polycarboxylicacids, alkyl glycerol sulphonates, fatty acyl glycerol sulphonates,fatty oleyl glycerol sulphates, alkyl phenol ethylene oxide ethersulphates, paraffin sulphonates, alkyl phosphates, isothionates such asthe acyl isothionates, N-acyl taurates, fatty acid amides of methyltauride, alkyl succinamates and sulphosuccinates, monoesters ofsulphosuccinate (especially saturated and unsaturated C12-C18monoesters) diesters of sulphosuccinate (especially saturated andunsaturated C6-C14 diesters), N-acyl sarcosinates, sulphates ofalkylpolysaccharides such as the sulphates of alkylpolyglucoside,branched primary alkyl sulphates, alkyl polyethoxy carboxylates such asthose of the formula RO(CH2CH20)_(k)CH2COO-M+ wherein R is a C8-C22alkyl, k is an integer from 0 to 10, and M is a soluble salt-formingcation, and fatty acids esterified with isethionic acid and neutralisedwith sodium hydroxide. Further examples are given in Surface ActiveAgents and Detergents (Vol. I and II by Schwartz, Perry and Berch).

The isotropic compositions of the present invention preferably compriseat least about 5%, preferably at least 10%, more preferably at least 12%and less than 70%, more preferably less than 60% by weight, of ananionic surfactant.

Alkyl sulphate surfactants, either primary or secondary, are a type ofanionic surfactant of importance for use herein. Alkyl sulphates havethe general formula ROS03M wherein R preferably is a C10-C24hydrocarbyl, preferably an alkyl straight or branched chain orhydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-C18alkyl or hydroxyalkyl, and M is hydrogen or a water soluble cation,e.g., an alkali metal cation (e.g., sodium potassium, lithium),substituted or unsubstituted ammonium cations such as methyl-,dimethyl-, and trimethyl ammonium and quaternary ammonium cations, e.g.,tetramethyl-ammonium and dimethyl piperdinium, and cations derived fromalkanolamines such as ethanolamine, diethanolamine, triethanolamine, andmixtures thereof, and the like.

Typically, alkyl chains of C12-C16 are preferred for lower washtemperatures (e.g., below about 50° C. and C16-C18 alkyl chains arepreferred for higher wash temperatures (e.g., about 50° C.). Alkylalkoxylated sulphate surfactants are another category of preferredanionic surfactant. These surfactants; are water soluble salts or acidstypically of the

formula RO(A)mSO3M wherein R is an unsubstituted C10-C24 alkyl orhydroxyalkyl group having a C10-C24 alkyl component, preferably aC12-C20 alkyl or hydroxyalkyl, more preferably C12-C18 alkyl orhydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero,typically between about 0.5 and about 6, more preferably between about0.5 and about 3, and M is hydrogen or a water soluble cation which canbe, for example, a metal cation (e.g., sodium, potassium, lithium,calcium, magnesium, etc.), ammonium or substituted-ammonium cation.Alkyl ethoxylated sulphates as well as alkyl propoxylated sulphates arecontemplated herein. Specific examples of substituted ammonium cationsinclude methyl-, dimethyl-, trimethyl-ammonium and quaternary ammoniumcations, such as tetramethyl-ammonium, dimethyl piperdinium and cationsderived from alkanolamines, e.g., monoethanolamine, diethanolamine, andtriethanolamine, and mixtures thereof. Exemplary surfactants are C12-C18alkyl polyethoxylate (1.0) sulphate, C12-C18 alkyl polyethoxylate (2.25)sulphate, C12-C18 alkyl polyethoxylate (3.0) sulphate, and C12-C18 alkylpolyethoxylate (4.0) sulphate wherein M is conveniently selected fromsodium and potassium.

The compositions of the present invention preferably comprise at leastabout 5%, preferably at least 10%, more preferably at least 12% and lessthan 70%, more preferably less than 60% by weight, of a nonionicsurfactant.

Preferred nonionic surfactants such as C12-C18 alkyl ethoxylates (“AE”)including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkylphenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy),block alkylene oxide condensate of C6 to C12 alkyl phenols, alkyleneoxide condensates of C8-C22 alkanols and ethylene oxide/propylene oxideblock polymers (Pluronic™-BASF Corp.), C8-C22 fatty acid methyl esterethoxylates, as well as semi polar nonionics (e.g., amine oxides andphosphine oxides) can be used in the present isotropic compositions. Anextensive disclosure of these types of surfactants is found in U.S. Pat.No. 3,929,678.

Alkylpolysaccharides such as disclosed in U.S. Pat. No. 4,565,647 arealso preferred nonionic surfactants in the isotropic compositions of theinvention.

Further preferred nonionic surfactants are the polyhydroxy fatty acidamides.

A particularly desirable surfactant of this type for use in theisotropic compositions herein is alkyl-N-methyl glucamide. Othersugar-derived surfactants include the N-alkoxy polyhydroxy fatty acidamides, such as C10-C18 N-(3-methoxypropyl)glucamide. The N-propylthrough N-hexyl C12-C18 glucamides can be used for low sudsing. C10-C20conventional soaps may also be used. If high sudsing is desired, thebranched-chain C10-C16 soaps may be used.

Another preferred anionic surfactant is a salt of fatty acids. Examplesof fatty acids suitable for use of the present invention include pure orhardened fatty acids derived from palmitoleic, safflower, sunflower,soybean, oleic, linoleic, linolenic, ricinoleic, rapeseed oil ormixtures thereof. Mixtures of saturated and unsaturated fatty acids canalso be used herein.

It will be recognised that the fatty acid will be present in the liquiddetergent isotropic composition primarily in the form of a soap.Suitable cations include, sodium, potassium, ammonium, monoethanolammonium diethanol ammonium, triethanol ammonium, tetraalkyl ammonium,e.g., tetra methyl ammonium up to tetradecyl ammonium etc. cations.

The amount of fatty acid will vary depending on the particularcharacteristics desired in the final detergent isotropic composition.Preferably 0 to 30%, more preferably 1-20 most preferably 5-15% fattyacid is present in the inventive isotropic composition.

Hydrotropes

Liquid detergent compositions according to the invention may besubstantially free from or may contain low levels of hydrotrope such aslow molecular weight primary or secondary alcohols exemplified bymethanol, ethanol, propanol, and isopropanol are suitable. Monohydricalcohols are preferred for solubilising surfactant. The compositions mayfor example contain from up to 15%, more especially from 0.2% to 8%,typically 0.5% to 8% by weight of hydrotrope material.

Clarity

The clarity of the isotropic compositions according to the presentinvention does not preclude the isotropic composition being coloured,e.g. by addition of a dye, provided that it does not detractsubstantially from clarity. Moreover, an opacifier could be included toreduce clarity if required to appeal to the consumer. In that case thedefinition of clarity applied to the isotropic composition according toany aspect of the invention will apply to the base (equivalent)isotropic composition without the opacifier.

Other Ingredients

Compositions according to the present invention preferably also containone or more other ingredients such as enzymes, enzyme stabilisers,bleaches (including bleach systems and components thereof).

Enzymes

“Detersive enzyme”, as used herein, means any enzyme having a cleaning,stain removing or otherwise beneficial effect in a laundry application.Enzymes are included in the present detergent compositions for a varietyof purposes, including removal of protein-based, saccharide-based, ortriglyceride-based stains, for the prevention of refugee dye transfer,and for fabric restoration. Suitable enzymes include proteases,amylases, lipases, cellulases, peroxidases, and mixtures thereof of anysuitable origin, such as vegetable, animal, bacterial, fungal and yeastorigin. Preferred selections are influenced by factors such aspH-activity and/or stability optima, thermostability, and stability toactive detergents, builders and the like. In this respect bacterial orfungal enzymes are preferred, such as bacterial amylases and proteases,and fungal cellulases.

Enzymes are normally incorporated into detergent or detergent additivecompositions at levels sufficient to provide a “cleaning-effectiveamount”. The term “cleaning effective amount” refers to any amountcapable of producing a cleaning, stain removal, soil removal, whitening,deodorizing, or freshness improving effect on substrates such asfabrics. In practical terms for current commercial preparations, typicalamounts are up to about 5 mg by weight, more typically 0.001 mg to 3 mg,of active enzyme per gram of the detergent composition. Statedotherwise, the compositions herein will typically comprise from 0.0001%to 10%, preferably from 0.001% to 5%, more preferably 0.005%-1% byweight of a commercial enzyme preparation.

Proteolytic Enzymes

Compositions according to the present invention may comprise one or moreproteolytic enzymes.

Endopeptidases (proteolytic enzymes or proteases) of various qualitiesand origins and having activity in various pH ranges of from 4-12 areavailable and can be used in the instant invention. Examples of suitableproteolytic enzymes are the subtilisins, which can be obtained fromparticular strains of B. subtilis, B. lentus, B. amyloliquefaciens andB. licheniformis, such as the commercially available subtilisinsSavinase™, Alcalase™, Relase™, Kannase™ and Everlase™ as supplied byNovo Industri A/S, Copenhagen, Denmark or Purafec™, PurafectOxP™ andProperase™ as supplied by Genencor International. Chemically orgenetically modified variants of these enzymes are included such asdescribed in WO-A-99/02632 pages 12 to 16 and in WO-A-99/20727 and alsovariants with reduced allergenicity as described in WO-A-99/00489 andWO-A-99/49056.

It should be understood that the protease is present in the liquiddetergent composition in a dissolved or dispersed form, i.e., theprotease is not encapsulated to prevent the protease from the liquidcomposition. Instead the protease in more or less in direct contact withthe liquid composition.

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B. licheniformis. Onesuitable protease is obtained from a strain of Bacillus, having maximumactivity throughout the pH range of 8-12, developed and sold asESPERASE™ by Novo Industries A/S of Denmark, hereinafter “Novo”. Thepreparation of this enzyme and analogous enzymes is described in GB1,243,784 to Novo. Other suitable proteases include ALCALASE™ andSAVINASE™ from Novo and MAXATASE™ from International Bio-Synthetics,Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756A, and Protease B as disclosed in EP 303,761 A and EP 130,756 A. Seealso a high pH protease from Bacillus sp. NCIMB 40338 described in WO9318140 A to Novo. Enzymatic detergents comprising protease, one or moreother enzymes, and a reversible protease inhibitor are described in WO9203529 A. Other preferred proteases include those of WO 9510591 A. Whendesired, a protease having decreased adsorption and increased hydrolysisis available as described in WO 9507791. A recombinant trypsin-likeprotease for detergents suitable herein is described in WO 9425583.

Useful proteases are also described in PCT publications: WO 95/30010, WO95/30011, WO 95/29979.

Preferred proteolytic enzymes are also modified bacterial serineproteases, such as those described in EP-A-251446 (particularly pages17, 24 and 98), and which is called herein “Protease B”, and inEP-A-199404, which refers to a modified bacterial serine proteolyticenzyme which is called “Protease A” herein, Protease A as disclosed inEP-A-130756.

The preferred liquid laundry detergent compositions according to thepresent invention comprise at least 0.001% by weight, of a proteaseenzyme. However, an effective amount of protease enzyme is sufficientfor use in the liquid laundry detergent compositions described herein.The term “an effective amount” refers to any amount capable of producinga cleaning, stain removal, soil removal, whitening, deodorizing, orfreshness improving effect on substrates such as fabrics. In practicalterms for current commercial preparations, typical amounts are up toabout 5 mg by weight, more typically 0.001 mg to 3 mg, of active enzymeper gram of the detergent composition. Stated otherwise, thecompositions herein will typically comprise from 0.001% to 5%,preferably 0.01%-1% by weight of a commercial enzyme preparation.Typically, the proteolytic enzyme content is up to 0.2%, preferably from4×10⁻⁵% to 0.06% by weight of the composition of pure enzyme.

Other Enzymes

Optionally the compositions of the invention may additionally oralternatively contain one or more other enzymes. For example, they maycontain 10-20,000 LU per gram of the detergent composition of alipolytic enzyme selected from the group consisting of Lipolase,Lipolase ultra, LipoPrime, Lipomax, Liposam, and lipase from Rhizomucormiehei (e.g. as described in EP-A-238 023 (Novo Nordisk).

The enzymatic detergent compositions of the invention further comprise10-20,000 LU per gram, and preferably 50-2,000 LU per gram of thedetergent composition, of an lipolytic enzyme. In this specification LUor lipase units are defined as they are in EP-A-258 068 (Novo Nordisk).

A further method of assessing the enzymatic activity is by measuring thereflectance at 460 nm according to standard techniques.

Suitable other enzymes for use in the compositions of the invention canbe found in the enzyme classes of the esterases and lipases, (EC3.1.1.*, wherein the asterisk denotes any number).

A characteristic feature of lipases is that they exhibit interfacialactivation. This means that the enzyme activity is much higher on asubstrate which has formed interfaces or micelles, than on fullydissolved substrate. Interface activation is reflected in a suddenincrease in lipolytic activity when the substrate concentration israised above the critical micel concentration (CMC) of the substrate,and interfaces are formed. Experimentally this phenomenon can beobserved as a discontinuity in the graph of enzyme activity versussubstrate concentration. Contrary to lipases, however, cutinases do notexhibit any substantial interfacial activation.

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.154, as disclosed in GB 1,372,034. See also lipases in JapanesePatent Application 53,20487. This lipase is available from AmanoPharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P“Amano,” or “Amano-P.” Other suitable commercial lipases includeAmano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosumvar. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan;Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. andDisoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.LIPOLASE™ enzyme derived from Humicola lanygiriosa and commerciallyavailable from Novo, see also EP 341,947, is a preferred lipase for useherein. Lipase and amylase variants stabilized against peroxidaseenzymes are described in WO 9414951 A to Novo. See also WO 9205249.Cutinase enzymes suitable for use herein are described in WO 8809367 Ato Genencor.

Because of this characteristic feature, i.e. the absence of interfacialactivation, we define for the purpose of this patent applicationCutinases as lipolytic enzymes which exhibit substantially nointerfacial activation. Cutinases therefor differ from classical lipasesin that they do not possess a helical lid covering the catalytic bindingsite. Cutinases belong to a different subclass of enzymes (EC 3.1.1.50)and are regarded to be outside the scope of the present invention.

Of main interest for the present invention are fungal lipases, such asthose from Humicola lanuginosa and Rhizomucor miehei. Particularlysuitable for the present invention is the lipase from Humicolalanuginosa strain DSM 4109, which is described in EP-A-305 216 (NovoNordisk), and which is commercially available as Lipolase™. Alsosuitable ar variants of this enzyme, such as described in WO-A-92/05249,WO-A-94/25577, WO-A-95/22615, WO-A-97/04079, WO-A-97/07202,WO-A-99/42566, WO-A-00/60063. Especially preferred is the variant D96Lwhich is commercially available from Novozymes as Lipolase ultra, andthe variant which is sold by Novozymes under the trade name LipoPrime.

The lipolytic enzyme of the present invention can usefully be added tothe detergent composition in any suitable form, i.e. the form of agranular composition, a slurry of the enzyme, or with carrier material(e.g. as in EP-A-258 068 and the Savinase™ and Lipolase™ products ofNovozymes). A good way of adding the enzyme to a liquid detergentproduct is in the form of a slurry containing 0.5 to 50% by weight ofthe enzyme in a ethoxylated alcohol nonionic surfactant, such asdescribed in EP-A-450 702 (Unilever).

The enzyme to be used in the detergent compositions according to theinvention can be produced by cloning the gene for the enzyme into asuitable production organism, such as Bacilli, or Pseudomonaceae,yeasts, such as Saccharomyces, Kluyveromyces, Hansenula or Pichia, orfungi like Aspergillus. The preferred production organism is Aspergilluswith especial preference for Aspergillus oryzae.

Other optional suitable enzymes which may be included alone or incombination with any other enzyme may, for example, be oxidoreductases,transferases, hydrolases, lyases, isomerases and ligases. Suitablemembers of these enzyme classes are described in Enzyme nomenclature1992: recommendations of the Nomenclature Committee of the InternationalUnion of Biochemistry and Molecular Biology on the nomenclature andclassification of enzymes, 1992, ISBN 0-12-227165-3, Academic Press. Themost recent information on the nomenclature of enzymes is available onthe Internet through the ExPASy WWW server (http://www.expasy.ch/).

Examples of the hydrolases are carboxylic ester hydrolase, thiolesterhydrolase, phosphoric monoester hydrolase, and phosphoric diesterhydrolase which act on the ester bond; glycosidase which acts onO-glycosyl compounds; glycosylase hydrolysing N-glycosyl compounds;thioether hydrolase which acts on the ether bond; and exopeptidases andendopeptidases which act on the peptide bond. Preferable among them arecarboxylic ester hydrolase, glycosidase and exo- and endopeptidases.Specific examples of suitable hydrolases include (1) exopeptidases suchas aminopeptidase and carboxypeptidase A and B and endopeptidases suchas pepsin, pepsin B, chymosin, trypsin, chymotrypsin, elastase,enteropeptidase, cathepsin B, papain, chymopapain, ficain, thrombin,plasmin, renin, subtilisin, aspergillopepsin, collagenase, clostripain,kallikrein, gastricsin, cathepsin D, bromelain, chymotrypsin C,urokinase, cucumisin, oryzin, proteinase K, thermomycolin, thermitase,lactocepin, thermolysin, bacillolysin. Preferred among them issubtilisin;

(2) glycosidases such as α-amylase, β-amylase, glucoamylase, isoamylase,cellulase, endo-1,3(4)-β-glucanase (β-glucanase), xylanase, dextranase,polygalacturonase (pectinase), lysozyme, invertase, hyaluronidase,pullulanase, neopullulanase, chitinase, arabinosidase,exocellobiohydrolase, hexosaminidase, mycodextranase,endo-1,4-β-mannanase (hemicellulase), xyloglucanase,endo-β-galactosidase (keratanase), mannanase and other saccharide gumdegrading enzymes as described in WO-A-99/09127. Preferred among themare α-amylase and cellulase; (3) carboxylic ester hydrolase includingcarboxylesterase, lipase, phospholipase, pectinesterase, cholesterolesterase, chlorophyllase, tannase and wax-ester hydrolase.

Examples of transferases and ligases are glutathione S-transferase andacid-thiol ligase as described in WO-A-98/59028 and xyloglycanendotransglycosylase as described in WO-A-98/38288.

Examples of lyases are hyaluronate lyase, pectate lyase, chondroitinase,pectin lyase, alginase II. Especially preferred is pectolyase, which isa mixture of pectinase and pectin lyase.

Examples of the oxidoreductases are oxidases such as glucose oxidase,methanol oxidase, bilirubin oxidase, catechol oxidase, laccase,peroxidases such as ligninase and those described in WO-A-97/31090,monooxygenase, dioxygenase such as lipoxygenase and other oxygenases asdescribed in WO-A-99/02632, WO-A-99/02638, WO-A-99/02639 and thecytochrome based enzymatic bleaching systems described in WO-A-99/02641.

Peroxidase enzymes may be used in combination with oxygen sources, e.g.,percarbonate, perborate, hydrogen peroxide, etc., for “solutionbleaching” or prevention of transfer of dyes or pigments removed fromsubstrates during the wash to other substrates present in the washsolution. Known peroxidases include horseradish peroxidase, ligninase,and haloperoxidases such as chloro- or bromo-peroxidase.

Peroxidase-containing detergent compositions are disclosed in WO89099813 A, Oct. 19, 1989 to Novo and WO 8909813 A to Novo.

A range of enzyme materials and means for their incorporation intosynthetic detergent compositions is also disclosed in WO 9307263 A andWO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S.Pat. No. 3,553,139, Jan. 5, 1971 to McCarty et al.

A process for enhancing the efficacy of the bleaching action ofoxidoreductases is by targeting them to stains by using antibodies orantibody fragments as described in WO-A-98/56885. Antibodies can also beadded to control enzyme activity as described in WO-A-98/06812.

A preferred combination is a detergent composition comprising of amixture of the protease of the invention and conventional detergentenzymes such as lipose, amylase and/or cellulase together with one ormore plant cell wall degrading enzymes.

Suitable amylases include those of bacterial or fungal origin.Chemically or genetically modified variants of these enzymes areincluded as described in WO-A-99/02632 pages 18,19. Commercial cellulaseare sold under the tradename Purastar™, Purastar OxAm™ (formerlyPurafact Ox Am™) by Genencor; Termamyl™, Fungamyl™, Duramyl™, Natalase™,all available from Novozymes.

Amylases suitable herein include, for example, alfa-amylases sescribedin GB 1,296,839 to Novo; RAPIDASE™, International Bio-Synthetics, Inc.and TERMAMYL™, Novo. FUNGAMYL™ from Novo is especially useful.

See, for example, references disclosed in WO 9402597. Stability-enhancedamylases can be obtained from Novo or from Genencor International. Oneclass of highly preferred amylases herein have the commonality of beingderived using site-directed mutagenesis from one or more of theBaccillus amylases, especialy the Bacillus cc-amylases, regardless ofwhether one, two or multiple amylase strains are the immediateprecursors.

Oxidative stability-enhanced amylases vs. the above-identified referenceamylase are preferred for use, especially in bleaching, more preferablyoxygen bleaching, as distinct from chlorine bleaching, detergentcompositions herein. Such preferred amylases include (a) an amylaseaccording to WO 9402597, known as TERMAMYL™,

Particularly preferred amylases herein include amylase variants havingadditional modification in the immediate parent as described in WO9510603 A and are available from the assignee, Novo, as DURAMYL™. Otherparticularly preferred oxidative stability enhanced amylase includethose described in WO 9418314 to Genencor International and WO 9402597to Novo Or WO 9509909 A to Novo.

Suitable cellulases include those of bacterial or fungal origin.Chemically or genetically modified variants of these enzymes areincluded as described in WO-A-99/02632 page 17. Particularly usefulcellulases are the endoglucanases such as the EGIII from Trichodermalongibrachiatum as described in WO-A-94/21801 and the E5 fromThermomonospora fusca as described in WO-A-97/20025. Endoglucanases mayconsist of a catalytic domain and a cellulose binding domain or acatalytic domain only. Preferred cellulolytic enzymes are sold under thetradename Carezyme™, Celluzyme™ and Endolase™ by Novo Nordisk A/S;Puradax™ is sold by Genencor and KAC™ is sold by Kao corporation, Japan.

Cellulases usable herein include both bacterial and fungal types,preferably having a pH optimum between 5 and 9.5. U.S. Pat. No.4,435,307 discloses suitable fungal cellulases from Humicola insolens orHumicola strain DSM1800 or a cellulase 212-producing fungus belonging tothe genus Aeromonas, and cellulase extracted from the hepatopancreas ofa marine mollusk, Dolabella Auricula Solander. Suitable cellulases arealso disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.CAREZYME™ (Novo) is especially useful. See also WO 9117243.

Detergent enzymes are usually incorporated in an amount of 0.00001% to2%, and more preferably 0.001% to 0.5%, and even more preferably 0.005%to 0.2% in terms of pure enzyme protein by weight of the composition.Detergent enzymes are commonly employed in the form of granules made ofcrude enzyme alone or in combination with other components in thedetergent composition. Granules of crude enzyme are used in such anamount that the pure enzyme is 0.001 to 50 weight percent in thegranules. The granules are used in an amount of 0.002 to 20 andpreferably 0.1 to 3 weight percent. Granular forms of detergent enzymesare known as Enzoguard™ granules, prills, marumes or T-granules.Granules can be formulated so as to contain an enzyme protecting agent(e.g. oxidation scavengers) and/or a dissolution retardant material.Other suitable forms of enzymes are liquid forms such as the “L” typeliquids from Novo Nordisk, slurries of enzymes in nonionic surfactantssuch as the “SL” type sold by Novo Nordisk and microencapsulated enzymesmarketed by Novo Nordisk under the tradename “LDP” and “CC”.

The enzymes can be added as separate single ingredients (prills,granulates, stabilised liquids, etc. containing one enzyme) or asmixtures of two or more enzymes (e.g. cogranulates). Enzymes in liquiddetergents can be stabilised by various techniques as for exampledisclosed in U.S. Pat. No. 4,261,868 and U.S. Pat. No. 4,318,818.

The detergent compositions of the present invention may additionallycomprise one or more biologically active peptides such as swolleninproteins, expansins, bacteriocins and peptides capable of binding tostains.

Enzyme Stabilisers

Compositions according to the present invention which contain one ormore enzymes also preferably contain at least one enzyme stabiliser.Such enzyme stabilisers may be selected from boron-containing proteaseenzyme stabilisers, non-boron protease enzyme stabilisers and mixturesthereof.

Boron-Containing Enzyme Stabilisers

Typical boron-based stabilisers include boron-based reversiblestabilisers which comprise a boron compound and another substancecapable of complexing with the boron compound to stabilise the enzyme inthe composition but which complexes dissociate in the wash liquor torender the enzyme active.

Suitable boron compounds include sodium metaborate or sodium tetraborate(borax).

Typical substances which form a reversible complex with the boroncompound including polyols such as glycerol, propylene glycol, andsorbitol. However, these are not enzyme stabilisers in the absence ofthe boron compound.

Typical inorganic boron sources are derivatives of boric acid includingboric oxide, polyborates, orthoborates and metaborates or mixturesthereof. Preferred compounds are the alkali salts of the boric acidderivatives, such as sodium borate and borax. Typical organic boronstabilisers are aromatic borate esters and boronic acid derivatives,such as alkyl, aryl and peptide boronic acids. Boronic acids arewell-known as reversible inhibitors for subtilisine type of proteases.

Another boron-based stabilising system which may be used is thecombination of boric acid or a boron compound capable of forming boricacid in the composition and a source of calcium ions, such as disclosedin EP-A-0 199 405.

Non-Boron Enzyme Stabilisers

Non-boron enzyme stabilisers include water soluble calcium compoundssuch as calcium chloride and/or formate and water soluble short chaincarboxylic acids, as well as sources of chlorine scavenge ions such asammonium sulphates, bisulphites, thiosulphites, thiosulphate and thiols.

Mixtures of one or more boron- and or non-boron enzyme stabilisers mayalso be based.

The total amount of enzyme stabiliser or stabiliser system is typicallyfrom 0.001% to 10%, preferably from 0.005% to 7.5%, especially from0.01% to 5% by weight of the total composition. Many non-boronstabilisers are protein inhibitors from various sources and modifiedpeptides (such as peptide aldehydes and peptide trifluoromethylketones). Suitable examples of these and other non-boron stabilisersinclude the following:—

WO-A-00/01826 discloses stabilized variants of Streptomycin subtilisininhibitor (protein inhibitor+variants).

WO-A-98/13459 discloses liquid detergents containing proteolytic enzyme,peptide aldehydes and calcium ions.

EP-A-0 583 534 discloses liquid detergents containing a peptidealdehyde.

EP-A-0 583 535 describes liquid detergents containing a peptidetrifluoromethylketone.

WO-A-97/00392 describes enzymatic compositions with improved storagestability of the enzymes contained therein are obtained by including anenzyme stabiliser, preferably by way of a particular process concernsthe use of lignosulphonates.

WO-A-00/01831 describes a fusion between a subtilisin and streptomycesinhibiors variants).

Another suitable class of non-boron enzyme stabiliser comprises thereversible protease inhibitors of peptide or protein type, e.g. asdisclosed in WO92/03529.

Further, our unpublished European Patent Application No. 00202092.3discloses other suitable non-boron enzyme stabilisers comprising atleast one saccharide selected from disaccharides, trisaccharides andderivatives of either as well as mixtures of these disaccharides,trisaccharides and derivatives.

Yet others are disclosed in WO-A-98/13458, WO-A-98/13460, WO-A-98/13461,U.S. Pat. No. 5,178,789, WO92/03529, WO-A-93/20175 and U.S. Pat. No.5,156,773.

Further non-boron compounds which may be incorporated as compounds whichare capable of stabilising proteases in liquids are organic substanceswhich form complexes with a transition metal, the complex being capableof catalysing bleaching of a substrate by atmospheric oxygen. Suchcompounds may be used as the free ligand and/or in complex with atransition metal, e.g. as disclosed in WO-A-00/12677. One specificligand of this kind isN,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-1-aminoethane. Yetother suitable non-boron protease stabilisers are polyoxometalates suchas disclosed in CA-A-2 183 814, EP-A-1 141 210 and WO-A-98/20101.

Bleaches

Optionally, any composition according to the invention may contain ableach or bleach system. Preferred are catalysts for bleaching byatmospheric oxygen.

Alternatively, oxygen bleaches and oxygen bleach systems may beemployed, for example in the form of an inorganic persalt preferablywith an activator, or as a peroxy acid compound.

In the case of the inorganic persalt bleaches, the activator makes thebleaching more effective at lower temperatures, i.e. in the range fromambient temperature to about 60° C., so that such bleach systems arecommonly known as low-temperature bleach systems and are well known inthe art. The inorganic persalt such as sodium perborate, both themonohydrate and the tetrahydrate, acts as release active oxygen nsolution, and activator is usually an organic compound havine one ormore reactive acyl residues, which cause the formation of peracids, thelatter providing for more effective bleaching action at lowertemperatures than the peroxy-bleach compound alone. The ratio by weightof the peroxy bleach compound to the activator is from about 15:1 toabout 2:1, preferably from about 10:1 to about 3.5:1. Whilst the amountof the bleach system, i.e. peroxy bleach compounds and activator may bevaried between about 5% and about 35% by weight of the total liquid, itis preferred to use from about 6% to about 30% of the ingredientsforming the bleach system. Thus, the preferred level of the peroxybleach compound in the composition is between 5.5% and about 27% byweight, while the preferred level of the activator is between about 0.5%and about 40%, most preferably between about 1% and about 5% by weight.

Typical examples of the suitable peroxybleach compounds are alkalimetalperborates, both tetrahdyrates and monohydrates, alkali metal,percarbonates, alkylhydroperoxides such as cumene hydroperoxide andt-butyl hydroperoxide, persilicates and perphosphates, of which sodiumperborate is preferred. Activators for peroxybleach compounds have beenamply described in the literature, including in British patentspecifications 836988, 855735, 907356, 907358, 907950, 1003310 and1246339, U.S. Pat. Nos. 3,332,882 and 4,128,494, Canadian patentspecification 844481 and South African patent specification 68/6344.

The exact mode of action of such activators is not known, but it isbelieved that peracids are formed by reaction of the activators with theinorganic peroxy compound, which peracids then liberate active-oxygen bydecomposition.

They are generally compounds which contain N-acyl or O-acyl residues inthe molecule and which exert their activating action on the peroxycompounds on contact with these in the washing liquor.

Typical examples of activators within these groups are polyacylatedalkylene diamines, such N,N,N¹N,¹⁻tetraacetylethylene diamine (TAED) andN,N,N¹,N¹⁻tetraacetylmethylene diamine (TAMD); acylated glycolurils,such as tetraacetylgylcoluril (TAGU); triacetylcyanurate and sodiumsulphophenyl ethyl carbonic acid ester.

A particularly preferred activator is N,N,N¹,N¹-tetraacetylethylenediamine (TAED). The activator may be incorporated as fine particles oreven in granular form, such as described in the applicants' UK patentspecification GB 2 053 998 A. Specifically, it is preferred to have anactivator of an average particle size of less than 150 micrometers,which gives significant improvement in bleach efficiency. Thesedimentation losses, when using an activator with an average particlesize of less than 150 μm, are substantially decreased. Even betterbleach performance is obtained if the average particle size of theactivator is less than 100 μm. However, too small a particle size cangive increased decomposition and handling problems prior to processing.However, these particle sizes have to be reconciled with therequirements for dispersion in the solvent (it will be recalled that theaforementioned first product from requires particles which are as smallas possible within practical limits). Liquid activators may also beused, e.g. as hereinafter described.

The organic peroxyacid compound bleaches (which in some cases can alsoact as structurants/deflocculants) are preferably those which are solidat room temperature and most preferably should have a melting point ofat least 50° C. Most commonly, they are the organic peroxyacids andwater-soluble salts thereof having the general formula

wherein R is an alkylene or substituted alkylene group containing 1 to20 carbon atoms or an arylene group containing from 6 to 8 carbon atoms,and Y is hydrogen halogen, alkyl, aryl or any group which provides ananionic moiety in aqueous solution. Such Y groups can include, forexample:

wherein M is H or a water-soluble, salt-forming cation.

The organic peroxyacids and salts thereof usable in the presentinvention can contain either one, two or more peroxy groups and can beeither aliphatic or aromatic. When the organic peroxyacid is aliphitic,the unsubstituted acid may have the general formula:

wherein Y can be H, —CH₃, —CH₂Cl,

And n can be an integer from 60 to 20. Peroxydodecanoic acids,peroxytetradecanoic acids and peroxyhexadecanoic acids are the mostpreferred compounds of this type, particularly 1,12-diperoxydodecandioicacid (sometimes known as DPDA), 1,14-diperoxytetradecandioic acid and1,16diperoxyhexadecandioic acid. Examples of other preferred compoundsof this type are diperoxyazelaic acid, diperoxyadipic anddiperoxysebacic acid.

When the organic peroxyacid is aromatic, a unsubstituted acid may havethe general formula:

wherein Y is, for example hydrogen, halogen, alkyl or a group as definedfor formulae (IV) above.

The percarboxy and Y groupings can be in any relative position aroundthe aromatic ring. The ring and/or Y group (if alkyl) can contain anynon-interfering substitutents such as halogen or sulphonate groups.Examples of suitable aromatic peroxyacids and saltes thereof includemonoperoxyphthalic acid, diperoxyterephthalic acid,4-chlorodiperoxy-phthalic acid, diperoxyisophthalic acid, peroxy benzoicacids and ring-substituted peroxy benzoic acids, such asperoxy-alpha-naphthoic acid. A preferred aromatic peroxyacid isdiperoxyisophthalic acid.

Another preferred class of peroxygen compounds which can be incorporatedto enhance dispensing/dispersibility in water are the anyhdrousperborates described for that purpose in the applicants' European patentspecification EP-A-217 454. Alternatively or in addition to, atransition metal catalyst may used with the peroxyl species, see, forexample WO-A-02/48301. A transition metal catalyst may also be used inthe absence of peroxyl species where the bleaching is termed to be viaatmospheric oxygen, see, for example WO-A-00/52124 and WO-A-02/48301.The transition metal catalysts disclosed in WO-A-00/52124 andWO-A-02/48301 are generally both applicable to what is known in the artas “air mode” and “peroxyl mode” bleaching. Another example of asuitable class of transition metal catalysts is found in WO-A-02/48301and references found therein.

It is also preferred to include in the compositions, a stabiliser forthe bleach or bleach system, for example ethylene diamine tetramethylenepholphonate and diethylene triamine pentamethylene phosphonate or otherappropriate organic phosphonate or salt thereof, such as the Dequestrange hereinbefore described. These stabilisers can be used in acid orsalt form which as the calcium, magnesium, zinc or aluminium salt form.The stabiliser may be present at a level of up to about 1% by weight,preferably between about 0.1% and about 0.5% by weight.

Since many bleaches and bleach systems are unstable in aqueous liquiddetergents and/or other interact unfavourably will other components inthe composition, e.g. enzymes, they may for example be protected, e.g.by encapsulation or by formulating a structured liquid composition,whereby they are suspended in solid form.

Other Optional Ingredients

The compositions herein can further comprise a variety of optionalingredients. A wide variety of other ingredients useful in detergentcompositions can be included in the compositions herein, including otheractive ingredients, carriers, hydrotropes, processing aids, dyes orpigments, solvents for liquid formulations, solid fillers for barcompositions, etc. If high sudsing is desired, suds boosters such as theC10-C16 alkanolamides can be incorporated into the compositions,typically at 1%-10% levels. The C10-C14 monoethanol and diethanol amidesillustrate a typical class of such suds boosters. Use of such sudsboosters with high sudsing; adjunct surfactants such as the amineoxides, betaines and sultaines noted above is also advantageous. Ifdesired, soluble magnesium salts such as MgCl₂, MgSO₄, and the like, canbe added at levels of, typically, 0.1%-2%, to provide additional sudsand to enhance grease removal performance.

Various detersive ingredients employed in the present compositionsoptionally can be further stabilized by absorbing said ingredients ontoa porous hydrophobic substrate, then coating said substrate with ahydrophobic coating. Preferably, the detersive ingredient is admixedwith a surfactant before being absorbed into the porous substrate. Inuse, the detersive ingredient is released from the substrate into theaqueous washing liquor, where it performs its intended detersivefunction.

By this means, ingredients such as the aforementioned, bleaches, bleachactivators, bleach catalysts, photoactivators, dyes, fluorescers, fabricconditioners and hydrolyzable surfactants can be “protected” for use indetergents, including liquid laundry detergent compositions.

Liquid detergent compositions can contain water and other solvents ascarriers.

Chelating Agents

The detergent compositions herein may also optionally contain one ormore iron, copper and/or manganese chelating agents. Such chelatingagents can be selected from the group consisting of amino carboxylates,amino phosphonates, polyfanctionally-substituted aromatic chelatingagents and mixtures therein, all as hereinafter defined.

If utilized, these chelating agents will generally comprise from about0.1% to about 10% by weight of the detergent compositions herein. Morepreferably, if utilized, the chelating agents will comprise from about0.1% to about 3.0% by eight of such compositions.

Clay Soil Removal/Anti-Redeposition Agents

The compositions of the present invention can also optionally containwater-soluble ethoxylated amines having clay soil removal andantiredeposition properties.

Liquid detergent compositions typically contain about 0.0 1% to about 5%of these agents.

One preferred soil release and anti-redeposition agent is ethoxylatedtetraethylenepentamine. Exemplary ethoxylated amines are furtherdescribed in U.S. Pat. No. 4,597,898,

Another type of preferred antiredeposition agent includes the carboxymethyl cellulose (CMC) materials. These materials are well known in theart.

Brightener

Any optical brighteners or other brightening or whitening agents knownin the art can be incorporated at levels typically from about 0.05% toabout 1.2%, by weight, into the detergent compositions herein.Commercial optical brighteners which may be useful in the presentinvention can be classified into subgroups, which include, but are notnecessarily limited to, derivatives of stilbene, pyrazoline, cournarin,carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles,5- and 6-membered-ring heterocycles, and other miscellaneous agents.Examples of such brighteners are disclosed in “The Production andApplication of Fluorescent Brightening Agents”, M. Zahradnik, Publishedby John Wiley & Sons, New York (1982).

Suds Suppressors

Compounds for reducing or suppressing the formation of suds can beincorporated into the compositions of the present invention. Sudssuppression can be of particular importance in the so-called “highconcentration cleaning process” as described in U.S. Pat. Nos. 4,489,455and 4,489,574 and infront-loading European-style washing machines.

A wide variety of materials may be used as suds suppressors, and sudssuppressors are well known to those skilled in the art. See, forexample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category ofsuds suppressor of particular interest encompasses monocarboxylic fattyacid and soluble salts therein. See U.S. Pat. No. 2,954,347. Themonocarboxylic fatty acids and salts thereof used as suds suppressortypically have hydrocarbyl chains of 10 to about 24 carbon atoms,preferably 12 to 18 carbon atoms. Suitable salts include the alkalimetal salts such as sodium, potassium, and lithium salts, and ammoniumand alkanolammonium salts.

The detergent compositions herein may also contain non-surfactant sudssuppressors. These include, for example: high molecular weighthydrocarbons such as paraffin, fatty acid esters (e.g., fatty acidtriglycerides), fatty acid esters of monovalent alcohols, aliphatic C 18-C40 ketones (e.g., stearone), etc.

The preferred category of non-surfactant suds suppressors comprisessilicone suds suppressors. This category includes the use ofpolyorganosiloxane oils, suchas polydimethylsiloxane, dispersions oremulsions of polyorganosiloxane oils or resins, and combinations ofpolyorganosiloxane with silica particles wherein the polyorganosiloxaneis chemisorbed or fused onto the silica. Silicone suds suppressors arewell known in the art and are, for example, disclosed in U.S. Pat. No.4,265,779.

For any detergent compositions to be used in automatic laundry washingmachines, suds should not form to the extent that they overflow thewashing machine.

Suds suppressors, when utilized, are preferably present in a “sudssuppressing amount”.

By “suds suppressing amount” is meant that the formulator of thecomposition can select an amount of this suds controlling agent thatwill sufficiently control the suds to result in a low-sudsing laundrydetergent for use in automatic laundry washing machines.

The compositions herein will generally comprise from 0.1% to about 5% ofsuds suppressor.

Fabric Softeners

Various through-the-wash fabric softeners, especially the impalpablesmectite clays of U.S. Pat. No. 4,062,647 as well as other softenerclays known in the art, can optionally be used typically at levels offrom about 0.5% to about 10% by weight in the present compositions toprovide fabric softener benefits concurrently with fabric cleaning. Claysofteners can be used in combination with amine and cationic softenersas disclosed, for example, in U.S. Pat. No. 4,375,416 and U.S. Pat. No.4,291,071. Also useable are the amphiphilic carboxy containing polymersas disclosed in US-A-2005/0124528.

Dye Transfer Inhibiting Agents

The compositions of the present invention may also include one or morematerials effective for inhibiting the transfer of dyes from one fabricto another during the cleaning process. Generally, such dye transferinhibiting agents include polyvinyl pyrrolidone polymers, polyamineN-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,manganese phthalocyanine, peroxidases, and mixtures thereof. If used,these agents typically comprise from about 0.01% to about 10% by weightof the composition, preferably from about 0.01% to about 5%, and morepreferably from about 0.05% to about 2%.

The invention will now be further illustrated by way of the followingnon-limiting examples:

EXAMPLES Example I Method:

The additives A-D are post-dosed to liquids 1-4 and incorporated bymixing. All prepared liquids are physical stable and transparent at roomtemperature. A panel of experts examines the physical stability andtransparency after 4 weeks of storage at 0 and 5° C. The observationsare described in table 1-4 and the panel used the following terms todescribe their observations.

Clear/no particles=transparent liquid without white particles, nodifference with liquids stored at room temperature.

Clear/small particles=transparent liquid with white particles formedduring storage. Hazy/no particles=during storage the liquid becomes nottransparent but there are no particles formed.

Hazy/white particles=during storage the liquid becomes not transparentand there are white particles formed.

TABLE I The physical stability of liquid 1 with different levelsadditives determined by a panel of experts after 4 weeks of storage at 0and 5° C. additive (see Physical stability Physical stability Table 7)level (%) (0° C.) (5° C.) None 0 hazy, small particles hazy, smallparticles A 0.5 hazy, small particles clear, small particles A 1 hazy,small particles clear, small particles A 2 hazy, small particles hazy,small particles B 0.5 hazy, small particles clear, small particles B 1hazy, small particles clear, small particles B 2 hazy, small particleshazy, small particles C 0.5 clear, small particles clear, no particles C1 clear, no particles clear, no particles C 2 clear, no particles clear,no particles D 0.5 hazy, small particles hazy, small particles D 1 Hazy,no particles hazy, small particles D 2 Hazy, no particles clear, noparticles

TABLE 2 The physical stability of liquid 2 with different levelsadditives determined by a panel of experts after 4 weeks of storage at 0and 5° C. Physical stability Physical stability additive level (%) (0°C.) (5° C.) None 0 Hazy, no particles clear, small particles A 0.5 Hazy,no particles clear, small particles A 1 Hazy, small particles clear,small particles A 2 Hazy, small particles clear, small particles B 0.5Hazy, small particles clear, small particles B 1 Hazy, small particlesclear, small particles B 2 Hazy, small particles clear, small particlesC 0.5 clear, no particles clear, no particles C 1 clear, no particlesclear, no particles C 2 clear, no particles clear, no particles D 0.5Hazy, small particles clear, small particles D 1 Hazy, small particlesclear, small particles D 2 Hazy, small particles clear, small particles

TABLE 3 The physical stability of liquid 3 with different levelsadditives determined by a panel of experts after 4 weeks of storage at 0and 5° C. Physical stability Physical stability Additive level (%) (0°C.) (5° C.) None 0 hazy, no particles hazy, small particles A 0.5 Clear,small particles hazy, no particles A 1 Clear, small particles clear,small particles A 2 Clear, small particles clear, small particles B 0.5Clear, small particles clear, small particles B 1 Clear, small particlesclear, small particles B 2 Clear, small particles clear, small particlesC 0.5 Clear, no particles clear, no particles C 1 Clear, no particlesclear, no particles C 2 Clear, no particles clear, no particles D 0.5Clear, small particles clear, small particles D 1 Clear, small particlesclear, small particles D 2 Clear, small particles hazy, small particles

TABLE 4 The physical stability of liquid 4 with different levelsadditives determined by a panel of experts after 4 weeks of storage at 0and 5° C. Physical stability Physical stability Additive level (%) (0°C.) (5° C.) None 0 Hazy, small particles hazy, small particles A 0.5Hazy, small particles clear, small particles A 1 Hazy, small particlesclear, small particles A 2 Hazy, small particles hazy, small particles B0.5 Hazy, small particles hazy, small particles B 1 clear, smallparticles hazy, small particles B 2 Hazy, small particles hazy, smallparticles C 0.5 clear, no particles clear, no particles C 1 clear, noparticles clear, no particles C 2 clear, no particles clear, noparticles D 0.5 Hazy, small particles hazy, small particles D 1 Hazy,small particles hazy, small particles D 2 clear, small particles clear,small particles

Example 2 Method:

Additive C is post-dosed to liquid 5 and incorporated by mixing. Allprepared liquids are physical stable and transparent at roomtemperature. A panel of experts examines the physical stability andtransparency after 8 weeks of storage at 0 and 5° C.

The observations are described in table 5 and the panel used thefollowing terms to describe theft observations.

Clear/no particles=transparent liquid without white particles, nodifference with liquids stored at room temperature.

Clear/small particles=transparent liquid with white particles formedduring storage. Hazy/no particles=during storage the liquid becomes nottransparent but there are no particles formed.

Hazy/white particles=during storage the liquid becomes not transparentand there are white particles formed.

TABLE 5 The physical stability of liquid 5 w/wo addition of additive Cdetermined by a panel of experts after 8 weeks of storage at 0 and 5° C.level Physical stability Physical stability Additive (%) (0° C.) (5° C.)None 0 hazy, small particles hazy, small particles C 1 clear, noparticles clear no particles

TABLE 6 composition liquids (as 100%) Liquid Liquid Liquid Liquid 1 (%)2 (%) 3 (%) 4 (%) Liquid 5 Monopropylene 1 1 1 1 0 glycol NaOH 1.49 1.171.64 1.53 1.45 Tinopal CBS-X 0.02 0.02 0.02 0.02 0.02 Citric acid 0.37 00.37 0 0.74 Dequest 2066 1 1 1 1 1 Nipacide BIT 20 LC 0.02 0.02 0.020.02 0.02 NeodoI25-7 E 7.18 7.17 8.18 8.16 7.66 Prifac 5908 1.70 1.701.70 1.70 1.69 LAS acid 7.18 7.18 8.18 8.16 7.66 SLES 3 EO 1.99 1.978.18 8.16 0 Relase 16 L ultra 0.38 0.38 0.38 0.38 0.38 Stainzyme 12 L0.10 0.10 0.10 0.10 0.10 Perfume 0.4 0.4 0.4 0.4 0.4 pH 8.3 8.3 8.3 8.38.3 Liquid A Liquid 6 Liquid B Liquid 7 (%) (%) (%) (%) Monopropylene 22 10 10 glycol NaOH 1.37 1.37 3.44 3.44 MEA 2.23 2.23 0 0 TEA 0 0 3.393.39 Tinopal CBS-X 0.02 0.02 0.02 0.02 NaCl 0.25 0.25 0 0 Citric acid 00 1.31 1.31 Dequest 2066 1 1 0 0 Proxel GXL 0.02 0.02 0 0 NeodoI 25-7 E4.45 4.45 14 14 Prifac 5908 8.00 8.00 5 5 LAS acid 9.0 9.0 21 21 SLES 2EO 0 0 7 7 LR400 0.2 0.2 0.25 0.25 PVPK15 0.1 0.1 0 0 Additive C 0 1.0 01 Water To 100 To 100 To 100 To 100 pH(±0.1) 8.3 8.3 8.3 8.3 Stability5° C. over Hazy Clear Hazy Clear 1 week

Materials:

LAS acid ═C10-C14 alkyl benzene sulphonic acid;

sLES 3 EO=sodium lauryl ether sulphate (with on average 3 oxide groups);

sLES 2 EO=sodium lauryl ether sulphate (with on average 2 oxide groups);

NI 7EO=C12-C13 fatty alcohol ethoxylated with an average of 7 ethyleneoxide groups; MPG=monopropylene glycol;

Prifac 7908=palmkernel fatty acid;

Proxel GXL=trade name biocide Proxel GXL (20% active)

Dequest 2066=diethylenetriamino-penta-(methylenenephosphonic acid)DETPMP

MEA=monoethanolamine

TEA=triethanolamine

Tinopal CBA-X=4,4-bis(2-disulfonic acid styryl) biphenyl PVPK15=polyvinylpyrrolidone K15

NaOH=Sodium hydroxide

NaCl=Sodium chloride

Nipacide BIT 20 LC=trade name Nipacide BIT 20 LC 20% active

Relase 16 L ultra=protease (relase 16 L ultra)

Stainzyme 12 L=amylase (stainzyme 12 L)

citric acid

perfume: commercial detergent perfume

TABLE 7 tested additives (referring to Formula (I)): additive R¹ and R²M (av.) n (av.) A C₁₂ alkenyl ca. 8 2 B C₁₂ alkenyl ca. 12 2 C C₁₈alkenyl ca. 12 2 D C₈ alkenyl ca. 12 2

1. An isotropic aqueous liquid detergent composition comprising: asuccinate dimer surfactant consisting of at least one compound offormula (I):

wherein in formula (I), each of R¹ and R² is independently selected fromalkyl and alkenyl groups having from 8 to 18, preferably from 12 to 18,most preferably 18 carbon atoms; each of R³ and R⁴ is independentlyselected from hydrogen, groups M where M is a metal counter-cation,preferably an alkali metal such as sodium, C₁-C₆, preferably C₁-C₄ alkylgroups and groups of formula —NR⁶R⁷ where R⁶ and R⁷ are independentlyselected from hydrogen and C₁-C₆, preferably C₁-C₄ alkyl groups; and R⁵is selected from poly(alkyleneoxy) groups, preferably groups of formula—(C_(n)H_(2n+1)O)_(m)—C_(n)H_(2n+1)— where m is from 0 to 12, preferablyfrom 6 to 10, more preferably from 8 to 10, most preferably 10 whereinin each C_(n)H_(2n+1) moiety n is independently from 2 to 4, morepreferably 2 and preferably also, each n is the same; one or more othersurfactants; and water.
 2. A composition according to claim 1, whereinR¹ and R² are independently selected from groups of formulaCH₃—(CH₂)_(p)—CH═CH—CH₂— where p is preferably from 4 to 14, morepreferably from 8 to 14 and most preferably is
 14. 3. A compositionaccording to claim 1, comprising from 0.1% to 5%, more preferably from0.2% to 3%, most preferably from 0.5% to 2% by weight of the disuccinatedimer surfactant.
 4. A composition according to claim 1, comprising from5% to 60%, more preferably from 10% to 50%, most preferably from 12% to45% by weight of the one or more other surfactants.
 5. A compositionaccording to claim 1, comprising from 30% to 90%, more preferably from40% to 85%, most preferably from 50% to 80% by weight of the water.
 6. Acomposition according to claim 1, further comprising soap.
 7. Acomposition according to claim 1, further comprising an atmosphericoxygen bleach catalyst.
 8. A method of preparing an isotropic liquiddetergent composition, the method comprising admixture of a succinatedimer surfactant according to claim 1, one or more other surfactants,water and optionally, one or more other ingredients.
 9. Use of asuccinate dimer surfactant according to claim 1, as a stabiliser for anisotropic liquid detergent composition comprising water and one or moreother surfactants.